DE2030589A1 - Telechelic oligomers for their preparation and process - Google Patents

Description

Merck Patent Society 2030589

limited liability June 11, 1970

Darmstadt

Telechelic oligomers ^1! ,
and methods of making them

It is known that, in the case of free-radically initiated polymerization, polymers with a broad molecular weight distribution arise, some of which carry fragments of initiator at the chain ends, but which are caused by termination and transfer reactions also have other end groups. . <

It is also known that the amounts of starter substance used have an influence on the molecular weight and the molecular weight range of the products obtained. In the usual polymerization, the initiators are added in amounts below 1 mole , based on the monomers, generally between 0.1 and 0.5 mole . The addition of larger amounts has already been described in individual cases. As a rule, however, the reactions are carried out in such a way that normal polymerization takes place.

In addition, a reaction is known in which a 20-30 molar excess of a free radical initiator with a monomer present in very dilute solution is described. Here However, it is a suppressed polymerization, since the radical fragment attaches itself directly to the monomer and thus polymerization does not take place at all.

It has now been found that, surprisingly, particularly valuable oligomers with identical groups on the two chain

10 985 2/19 72

tending (teleehele oligomers) in high yields can, if the corresponding monomers are reacted with much larger amounts of symmetrical initiators than they are normally used for polymerizations. In this way, a quick and even chain termination is obtained and thus oligomers with a relatively narrow molecular weight distribution; and with defined and identical groups both ends of the chain. The formation of products with identical end groups takes place surprisingly under these reaction conditions even if the chain is terminated by disproportionation under conventional polymerization conditions (e.g. Journal Polymer Science, Volume 12, page 449 ff (1954) and Zeitschrift für Physikalische Chemie, Volume 27, page 1 ff, (1961)).

The radicals should be present in sufficient quantity during the reaction in order to achieve the desired degree of polymerization Always block both ends of the chain equally. The concentration of the initiator fragments must therefore be matched to the polymerization rate of the monomers so that the desired degree of polymerization a complete chain termination can take place by identical initiator radicals. Amazingly, at least for that easily radically polymerizable monomers this vote can be achieved solely through the presence of the appropriate amount of initiator fragments. In this way you can adjust the degree of polymerization of the resulting telechelic oligomers relatively precisely in a very simple and elegant manner.

From the previously known reactions between polymerizable This course of the reaction could not have been foreseen for monomers and the radical donating azo compounds. So inabe-

109862/1972

In particular, from the formation of bifunctional derivatives from butadiene and azo compounds, it cannot be concluded that monovinyl compounds and / or compounds which are difficult to polymerize from a radical point of view can be converted in this way into telechelic oligomers with a predeterminable chain length. In the case of butadiene, the 1,4-addition mechanism normally predominates, so that the addition of the radicals in the 1,4-position was to be expected. The radical sites with an allyl structure that are located at the chain end during the polymerization of butadiene are resonance-stabilized and are therefore more capable than other monomers of chain termination through combination. In the case of mono-olefins, on the other hand, only one 1,2-addition is possible. Given the known ease with which growing radical chains of such monomers n in turn add monomers and taking into account the fact that the polymerization process is terminated to a not inconsiderable extent by chain transfer and disproportionation, the chain termination is exclusively through radical fragments according to the method of present invention surprising. It was also already known to polymerize a mixture of ethylene and 3 »3-dimethyl-butene (1) using azoisobutyrodinitrile (AIBN). However, copolymers with 1-2 functional end groups are only formed in very low yields (about 3 to at most 30 #). According to this publication, higher yields are not possible. Nor can it be inferred from it that, in general, monovinyl compounds in which the chain is terminated partly by disproportionation lead very uniformly to products with two identical end groups and with a narrow molecular weight distribution.

The present invention thus offers a completely new way in a technically very simple manner and in a very good yield

109852/1972

the various monomers telechelic oligomers with defined and to produce predictable chain lengths that are exclusive, bifunctional.

• The invention is a method for the production of telechelic oligomers with 2 identical groups on the two Chain ends, which consists in the fact that one radically polymerizable monovinyl compounds with the exception of olefins with more as 2 carbon atoms with a symmetrical, radical donating azo compound, the concentration of the initiator fragments is adjusted so that when the desired degree of polymerization between 1 and 200 is reached, a complete The chain is terminated exclusively by fragments of the initiator. The amount of initiator is between 0.5 and 50 mol $, based on the monovinyl compounds used.

The invention also relates to telechelic oligomers with an average degree of polymerization of 1 to 200, the chains of which are monovinyl compounds except olefins with more than 2 C atoms are the basis and both ends of the chain consist of identical radical fragments, which consist of radical donating, symmetrical azo compounds.

109852/1972

.5 -

The most technically accessible connections can be by characterizing the formula I:

"~ Ο - / I η

- / —R

wherein

R is the radical fragment of a symmetrical azo compound

manure.

R _{1 is} hydrogen or lower alkyl, in particular methyl Rp is hydrogen, phenyl or substituted phenyl,

-GOOR ₅ , -COR., -CHO, -CIi, or -ORc R, hydrogen; Alkyl with up to 18 carbon atoms, which can also be interrupted by heteroatoms (O, N, S)?

Cycloalkyl with 3-7 carbon atoms; Phenyl and substituted phenyl;
R. UH ₉ and the associated mono- and dialkyl derivatives (alkyl groups with up to 18 carbon atoms); CO-alkyl (alkyl groups with up to 18 carbon atoms) and CO-phenyl-.

where the phenyl groups can also be substituted; Alkyl or aliphatic acyl, each with up to

18 carbon atoms;

a number between 1 and 200

η means

with the proviso that there is material.

is not alkyl when R ₂ . water

Telechelic oligomers are also of particular importance Formula II.

R - (CH ₂ - CH) _n - R
^R 2

10985 2/19 72

R is the radical fragment of a symmetrical azo compound R _{2 is} hydrogen or phenyl η 1 - 200

-Λ

means, as well as telechelic oligomers of the formula III

R - (CH ₂ -O) -H

H ^II3C '

R is the radical fragment of a symmetrical azo compound R _{1 is} hydrogen or methyl R ₆ COO-alkyl with up to 18 carbon atoms; CONH ₂ , .CHO or CN

η 1 - 200
means. ·

Finally, telechelic oligomers of the formula IV are also R - (CH ₂ - CH) _ - R

IV

R and η die. Have the meaning given above, of special interest.

With regard to the accessibility of the starting materials are

in detail the telechelic oligomers of the formula V PH »CH _x

NC-C- (CH ₂ - CH ₂ ) _n - C - CN _y CH ₅ 'CH ₅

where η is a number between 5 and 150, of formula VI

109852/1972

CH * 'CH,

ι ■ '■ ι ³

NG-C- (CH ₂ - CH) _n - C - CU

VI

CH ₃ , yj CH ₃

where η is a number between 1 and 50, and the formulas VII and VIII

-J CHrj CHijc

I ³ I ³ I '

NC-C (CH ₂ - C) _n - C- CN III

II COOCH ₃ CH ₃

CH ₃

NC - C - (CH ₀ - CH L - C - CN '

j ² Il ^VI11

CH ₃ COOCH ₃ CH ₃

where η is a number between 1 and 50,

109862/1972

It is essential to carry out the reaction in the presence of sufficiently large amounts of free radicals. With slightly radical polymerizable monomers should therefore, for. B. the azo compound decomposed to radicals within the shortest possible time in the presence of the monomers or the oligomers formed therefrom will. Thermal decomposition of the azo compounds is preferred.

In principle, all symmetrical azo compounds which are usually used for free-radically initiated polymerizations can be considered as free radical donors. As a rule, use will be made of those azo compounds which decompose into the radicals with sufficient speed ^{within the temperature range of 60-16O 0 C.} The temperatures required for the thermal decomposition of the azo compounds depend on the thermal stability (half-life) of the azo compounds.

These half-lives are known or can be easily modified using standard methods be determined. The half-life of the azo compounds to be used according to the invention should be within the specified temperature range at a maximum of 120 minutes.

In addition, the azo compounds to be used here should be symmetrical be structured so that telechelic products with identical end groups are created.

In principle, instead of the thermal decomposition of the azo compounds, photolytic decomposition by high-energy Rays, e.g. B. UV light. Except the

109852/1972

"Λ

However, there is a cost for such a photolytic reaction Thermal splitting is also preferred because the simultaneous formation of larger amounts of radicals is better controlled thermally can be.

Azqdinitriles are most frequently used as initiators, z. B. azo compounds of the formula

OH, CH

3 ι

CH ι 5

«■ ν -.c -

cn -c - -Ν «■ ν -.c - on

in which.

'R ₁ denotes lower alkyl, in particular methyl or ethyl.Von die-; Azoisobutyrodinitrile (AIBN) is particularly preferred because of its easy technical accessibility. However, there are also a number of other azo compounds known as free radical donors, e.g. B. azo dicarboxylic acids, azodicarboxylic acid esters and azo compounds which are symmetrically substituted by aryl, alkyl or aralkyl groups. The following are specifically mentioned as examples:

2,2'-azo-bis-isobutyronitrile (ΑΙΒΪΓ)

2,2'-azo-bis-2-methylbutyronitrile;

2,2'-Azo-bis-isobutyric acid alkali salts, the associated amide and the esters, especially the corresponding methyl and; * Ethyl ester j

2.2 ^t -azo-bis-2-methylbutyric acid alkali salts, the associated amide and the esters, especially the corresponding methyl; and ethyl ester. j

4,4'-Azo-bis-4-cyanopentanoic acid, its di-Na-salts and its alkyl esters,
4,4'-azo-bis-4-cyano-pentanol- (1)

109852/1972

1,1'-azo-dicyclopentanecarbonitrile

1,1'-azodicycrohexanecarbonitrile

2,2'-Azobis (a-cyclopropylpropionitrll) 2,2'-azo-bis-cyclopentylpropionitrile 2,2'-azobis (a-cyclohexylpropionitrile) 1,1'-azodicamphan carbonitrile

β, β'-azobis-ß-cyano-propanesulfonic acid and its di-Na salt 2,2 '-Azobis (α, γ-dimethylvaleronitrile)' 2,2'-azo-bis-2-benzyl-propionitrile

2,2'-azo-bis-2- (4-chlorobenzyl) propionitrile 2,2'-azo-bis-2- (4-nitrobenzyl) propionitrile 2,2'-azo-bis-2-ph.enyl-propionitrile

2,2'-azo-bis-2- (4-methoxyphenyl) propionitrile 2,2 · azo-bis-2- (4-bromophenyl) propionitrile 1,1'-azo-bis-1-chloro-1-phenylethane

1,1 * -Azo-bis-1 - (p-meth.oxyphenyl) -ethan 1,1'-azo-bis-1-phenylethane

Azo-bis-diphenylmethane

α, α'-azobis (α-methylene-anthronitrile) Perfluoroazopropane

Perfluoroazobutane

Depending on the azo compound used, the telechelic oligomers obtained are ζ. Β. α, Oi -Dinitriles, -dicarboxylic acid esters or -dicarboxylic acids or else

Diaryl, dialkyl or diaralkyl telechelics, which optionally contain further substituents. Preferred azo compounds are those which are telechelic oligomers with functional Deliver groups.

Because of their easy accessibility, preference is given to those symmetrical azo compounds which provide the radicals a - c:

109852/1972

SLj

b) E ₇ c)

• C - ON '«C - COOB ₈ # 0 - ■ OH ₂ -CH ₂ -COOR ₉

where *

Methyl or ethyl.; .-. ·. '

an alkyl radical with up to 6 carbon atoms and Means hydrogen, an alkali metal or an alkyl radical with Ms to 6 carbon atoms.

The amount of initiator to be used is, as already stated above, between 0.5 and 50 mol #, based on the monomers used. Pure styrene and its derivatives and for acrylic and methacrylic derivatives are generally preferred in amounts between 2 and 50 mol $.

In principle, all free-radically polymerizable monomers can be used as monomers Monovinyl compounds are used with the exception of olefins with more than 2 carbon atoms. As for the inventive The only decisive factor is the concentration ratio of the starter or the free radicals to the monomers, the monomers can be varied very widely. Most importantly are of course the monomers most commonly used technically, i.e. in particular ethylene, styrene and derivatives, Tetrafluoroethylene and acrylic and methacrylic derivatives. A row of the most important monovinyl compounds can be characterized by the following formula JL:

CH ₂ = C - R ₂ A

in which R ₁ and E _{2 have} the meaning given in formula I and in which R _{1 is} not alkyl when R _{2 is} hydrogen.

If the radical R ₂ here contains substituted phenyl groups, these substituents on the phenyl ring can of course be varied very widely. Examples include: alkyl and acoxy groups with up to 18 carbon atoms, which are also

109852/1972

to know to be broken; Halogens such as fluorine, chlorine and bromine; Hydroxy; Nitro .; Amino as well as mono- and dialkylamino; Aryl and aryloxy, in particular phenyl and phenoxy and phenoxyalkyl; COOR, or COR., Where R, and R. have the meaning given in formula 'I. As a rule there are 1 to 3 of these substituents on the phenyl ring available. <

In addition to styrene itself, the substituted styrenes are also suitable, in particular alkyl (preferably methyl) -substituier- ■■ te styrenes, where the alkyl groups, especially a methyl group, can sit on the core as well as on the chain. but Halogen- and alkoxy-substituted styrenes also play a role.

Among the acrylic and methacrylic derivatives which are of industrial importance, there are in particular the esters of the acrylic and the '. Methacrylic acid with up to 18 carbon atoms called, it being possible for the alkyl chains of these esters to be interrupted by cycloaliphatic radicals (eg, cyclohexyl) or by heteroatoms. This subheading includes B. derivatives such as dimethylaminoethyl ester or ethoxyethyl ester. The phenyl and cresyl esters also deserve a mention. It is also known that acrylic and methacrylamides and their N-alkyl derivatives are of importance, of which the N-mono- and N-dialky compounds with up to 18 carbon atoms in the alkyl radical are the best known. Finally, acrylic nitrile, methacrylonitrile and acrolein also play an important role as "technically easily accessible, free-radically polymerizable: monovinyl compounds.

Particular mention should also be made of vinyl ketones, of which the Alkyl vinyl ketones are of the greatest importance, for example methyl vinyl ketone and ethyl vinyl ketone. But phenyl vinyl ketone is also of interest. ·;

In addition to tetrafluoroethylene, other halogenated alkenes can also be used, e.g. B. trifluorochloroethylene and difluorodichloroethylene, also vinyl chloride, bromide and fluoride, vinylidene chloride and vinyl esters, especially those

109852/1972

Esters of vinyl alcohols with aliphatic carboxylic acids with 1 18, preferably 1-6 carbon atoms, ζ. B. vinyl acetate, vinyl propionate and butyrate. The vinyl ethers with alkyl groups with up to 18 carbon atoms are also of interest.

Finally, monoviny compounds which can be used according to the invention are also unsaturated aliphatic dicarboxylic acids with preferably no more than 6 carbon atoms and their functional derivatives such as salts, esters, anhydrides, nitriles and amides. Examples are maleic acid and itaconic acid and their anhydrides mentioned. However, maleic acid and its derivatives are preferred used in combination with other monomers.

Silicon compounds containing vinyl groups can also be used as monomers can be used. Of particular importance are alkoxy and aryloxy vinyl silanes, where z. B. triethoxyvinylsilane e.ines of the most common products. ■

Furthermore, vinyl-containing heterocycles come into consideration, among which, for. B. N-vinylpyrrolidone, N-vinylimidazole and N-vinylphthalimide as well as vinyl pyridine, vinyl quinoline and vinyl thiophene are of importance. ■

Of course, mixtures of the above can also be used in each case Monomers are used. This provides a further possibility to improve the properties of the telechelic oligomers, e.g. Melting range or viscosity to change in a targeted manner. So z. B. the melting point of the oligoethylenes with nitrile end groups Copolymerization of ethylene and vinyl acetate can be significantly reduced. Ethylene, styrene and vinyl esters and ethers are particularly suitable for the joint reaction with other monomers.

The oligomerization itself can be carried out by any conventional method be carried out, that is, in bulk, in solution, in suspension or in emulsion. One is preferred

109852/1972

Polymerization in solution, because in this way the heat dissipation can be regulated more easily. When using solvents however, care must be taken to ensure that these do not cause any or at least no significant chain transfer. Also must the solvent on the initiator sien, because this should be in the chosen solvent at the reaction temperature have sufficient solubility.

Suitable solvents are e.g. B. hydrocarbons such as benzene, toluene or xylene; aliphatic ^ alcohols such as methanol, Ethanol or, in particular, tert-butanol; Nitriles, especially acetonitrile and adiponitrile; Ethers such as tetrahydrofuran and / or dioxane; Ketones such as acetone or cyclohexanone, furthermore Esters such as B. ethyl acetate or n-butyl acetate. All Solvents can be used individually or as a mixture.

The Eeakbion itself is conducted in such a way that the existing The amount of initiator to be converted into monomers reacts as completely as possible in a short time. The shorter the decomposition time kept the lower the non-uniformity of the oligomers with respect to the molecular weight distribution. The splitting of the Initiator should therefore take place as completely as possible in the shortest possible time. The shorter this decomposition time is kept, the more uniform are the resulting oligomers.

It is expedient to use the one corresponding to the desired degree of polymerization To heat the amount of azo compound together with the monomers at least to a temperature at which the half-life the initiator disintegration is about 4 hours.

The decomposition temperatures of the azo compounds are known. The breakdown into radicals begins z. B. for AIBN at about 5O ⁰ G and has already reached a considerable extent at about 80 °. In the case of monomers which polymerize very quickly, it is therefore expedient to heat the reaction mixture very quickly to at least this decomposition temperature of the initiator. That

109852/1972

can ζ. B. be carried out in such a way that the reaction coefficients components together or separately, e.g. into a solvent heated to the required decomposition temperature. There are particular advantages if you pass the reaction components through a thin llohr, z. B. a metal pipe that pumps up the required temperature is heated. The dwell time in the heated zone of such a tube or such a capillary can be adjusted by routine experiments so that oligomers with a very uniform degree of polymerization are formed. In many cases it is convenient to combine the monomers metered continuously with the initiator into a preheated tube, which may already contain solvent. '

Surprisingly, the average degree of polymerization of the resulting oligomers can be controlled relatively precisely solely through the ratio of initiator to monomer concentration. The optimum free radical concentration in each case depends on the willingness to polymerize (and thus also the rate of polymerization under the given conditions) of the respective monomers. Large polymerization require the same high radical concentrations · If you only ensures that a sufficiently high concentration is present in free radicals, so it is also worn for an almost complete splitting of the azo compound into radicals worry, g is just the amount of initiator decisive for the degree of polymerization of the resulting telechelic oligomers. The reaction is usually quantitative. Therefore z. B. an average degree of polymerization of about 10, if one uses 10 mol # of the azo compound, based on starting monomers such as styrene or ethylene. On the other hand, at 20 mol # the degree of polymerization is about 5, while at 3 mol # initiator telechelic oligomers with an average degree of polymerization of about 33 are formed. However, this reciprocal linear dependence applies strictly only to those monomers which are known to be easily polymerizable by radical initiation. Monomers that are relatively bad

109852/1972

by. Radicals, especially those made from azo compounds, which are polymerizable, therefore lead under the same conditions to telechelic oligomers with shorter chains. For example, the same monomer / initiator ratio in the case of styrene which is easily polymerizable by free radicals results in a higher average degree of polymerization than, for example, in the case of oc-methylstyrene, which is more difficult to polymerize in free radicals. However, since the reactivity of the individual monomers in free-radical polymerizations is known from the literature, the desired chain lengths can easily be predetermined and set even for slower polymerizing monomers. Monomers which are polymerizable hardly radical initiation (eg., Vinyl _ether)} products result this low polymethyl "risationsgrad because of rapid or immediate chain termination

is preferred by initiator radicals. In such cases it is advantageous to lower the radical concentration of initiator to increase, d. H. not to split the azo compounds completely into radicals too quickly.

Working up the mixture obtained after the polymerization takes place in a conventional manner. If solvents have been used, these are preferably reduced Pressure removed. At the same time, at least some of the by-products caused by decomposition of the Initiators have emerged, e.g. B. Tetramethylsuccinic acid & · Dinitrile when using AIBN. In many cases it is also expedient to treat the oligomers obtained in a high vacuum (about 1 Torr), if necessary at elevated temperatures (e.g. 40 - 80 <kJ) to connect to further solvent residues and remove unwanted accompanying substances.

109852/1972

- primal

The telechelic oligomer mixtures obtained are exclusively 1) i-functional, ie both ends of each chain are always substituted by the same initiator fragments. The values for the number average molecular weight determined by end group analysis and vapor pressure osmometry agree very well within the error limits. The uniformity of the oligomers which can be prepared according to the invention can be demonstrated even more precisely by separation by gel chromatography. If only 1 <fo of the oligomer mixture had a different end group, this would be evident from the gel chromatogram. ·

The products obtained are of great technical interest because of their identical functional end groups and the degree of polymerization which can be precisely adjusted by varying the amounts of initiator. You can e.g. B. be used as intermediate products in the plastics industry. In addition, the telechelic oligomers obtainable according to the invention are also valuable technical products themselves, which are used in many different ways because of the easily adjustable chain length of the oligomers. So are z. B. in particular the dinitriles and diesters are well suited as plasticizers, as hydraulic fluids, machine oils, additives to paints and as formulation auxiliaries. The dicarboxylic acids according to the invention can, for. B. as salts, also as stabilizers for plastics, as metal soaps and as net- | and emulsifiers are used. In general, the telechelic oligomers according to the invention can also be used particularly well as functional fluids, e.g. B. for heat transfer, as cooling liquids and / or lubricants, can be used. As lubricating oil additives partially have even corrosion inhibiting properties ·

109852/197 2

The values for the average molecular weights given in the following examples are, unless otherwise stated, has been determined by means of vapor pressure osmotics.

Example 1 ■■

104 g (1 mol) of styrene and 16.4 g (0.1 mol) of AIBN are in 500 ml Benzene dissolved. The reaction mixture quickly boils heated and refluxed for about 8 hours. The solvent is then removed on a rotary evaporator. That remaining oligomer mixture of the formula

(YH ₃

NC-C-CH "- CH 4 C-CN

CH ₃

has a waxy consistency. It has an NG content of 2.5 $, this corresponds to an average degree of polymerization of η = 9. The gel chromatographic analysis shows that there is a strictly polymer-homologous series, ie that only products with identical end groups are present.

Example 2

A solution of 32.8 g (0.2 mol) of AIBN in 104 g (1 mol) of styrene is added dropwise to 500 ml of boiling toluene in the course of 4 hours. The solution obtained can either be used as such for further reaction of the oligomers formed or the oligomers can be isolated by evaporating off the solvent.
Average degree of polymerization n: 4 »7
N content: 4.5 #

109852/19 72

Example 3 '

A solution of 150 g of AIBI (0.9 mol) and 1040 g of styrene (10 mol) in 3 l of toluene is slowly pumped through thin (0 1.1 mm) externally heated steel pipes. The residence time of the solution in the heated zone (10O ⁰ O) is about 15 minutes. ·

The solution obtained is made by removing the solvent telechelic oligomers with the following characteristics are obtained:

Texture: waxy products
average degree of polymerization n: 10 ■ H content: 2.5 wt. #

The degree of polymerization can be reduced by reducing the Set initiator content to 1/5 to η = 50. .

Example 4

A solution of 104 g of styrene and 32.6 g of AIBN "in 1 l of toluene is pumped through a 1.1 mm thick capillary at a rate of 40 ml / hour. The capillary is 15 m long, wound into a spiral and located in a ^{thermostat heated to 100 °} C. The toluene and unconverted styrene are removed on a rotary evaporator. The residue has an IT content of 6.21 °; this corresponds to an NL value of 451 with 2 nitrile end groups in the molecule. Vapor pressure osmometry gives an ML = 454 (n = 3). The gel chromatographic analysis shows that the mixture contains less than 3% by weight of oligomers with molecular weights above 2500.

Example 5

16.4 g (0.1 mol) of AIBN in 250 ml Dissolved methanol. The autoclave is flushed with nitrogen and

109852/1972

exposed to ethylene up to a pressure of 50 atü (at 5 ⁰ O). The autoclave is ^{kept at 80 °} C. for 12 hours. It is then cooled to room temperature and the oligomers formed are filtered off from the solvent. 135-140 g of a crystalline product of the 3-shape are obtained

CH ₅

C-CN CH,

with a Sehmelzbereich 96-99 ⁰ C. The IR spectrum includes the characteristic nitrile band. Average degree of polymerization 5. = 84
N content: 1.10%, corresponding to a ΐ ^ value of 2450; M _n (rest) 2500

If 8.2 g (0.05 mol) of AIBN are used under otherwise identical reaction conditions, a reaction product is obtained η = 160.

Example 6

32.8 g of AIBN and 250 ml of methanol are filled into a 1 l autoclave, which is freed of oxygen _{by repeatedly forcing in N 2 and ethylene.} Are pressed 6 moles (about 50 atm) ethylene and heats for 6 hours at 80 ⁰ C. The reaction product (100-110 g). Is separated by filtration and recrystallized from dioxane. Melting range: 62 - 68 C; η =. N content $ 2.57> \ this corresponds to an I ^ value of 1090; * M _n (rest) = 1000.

Example 7

A mixture of 142.1 g (1 mol) of butyl methacrylate, 16.4 g (0.1 mol) of AIBN and 500 ml of benzene are 6 Heated at reflux for hours. After distilling off the lo-

10985 2/1972

The viscous residue obtained in quantitative yield by solvent has an N content of 1.5 % and an average M of 1850. ·
5 = 12

Example 8 ■>''

25 g (0.25 mol) of ethyl acrylate and 4.1 g (0.025 mol) of AIBN are dissolved in 125 ml of benzene. The mixture is placed in an oil bath preheated to 120 ° and boiled under nitrogen for 8 hours. The solvent is then stripped off under reduced pressure. 29 g of an oligomeric mixture with an M _n 1210 and an N content of 2.3 # are obtained. The average degree of polymerization is η. ■ «11.

Example 9

85.5 g of styrene (0.822 mol) are dissolved in 2.5 l of toluene. In the so. obtained solution is suspended 23 g (0.082 mol) of 4 »4'-AzO ^ Is 4-cyanopentanoic acid and the suspension is added dropwise to 100 ml of boiling toluene over a period of 4 hours with constant stirring. Then After one hour, the mixture is heated under reflux, allowed to cool, insolubles are filtered off and the solvent is added in a vacuum. Do you get a viscous oil? η = 8.. Analysis:

calculated:

found:

Example 10 |

Analogously to Example 8, 32.5 g (0.25 mol) of 4-methoxystyrene are reacted with 4.1 g (0.025 mol) of AIBH in 125 ml of benzene. A colorless syrup with a U content of $ 2.2 is obtained. M _n 1170; η a 9 - 10

Example 11

26 g (0.25 mol) styrene and 4.8 g (0.025 mol) 2,2'-azo-bis- (2-

C. H IT 0 M. 84.1 7.4 2.6 5.9 1084 84.5 7.9 2.5 6.0 1035

1098 52/1972

methylbutyronitrile) are reacted in 125 ml of toluene as in Example 8. A glassy residue with an N content of 2.4 <$> is obtained.
M _n = 1200 ^

ή = 10

Example 12 '

47.6 g (0.25 mol) of triethoxyvinylsilane are dissolved together with 4> 1 g (0.025 mol) of AIBN in 70 ml of benzene. This solution is added dropwise to 50 ml of boiling benzene in the course of 2 hours. The mixture is then refluxed for a further hour, the solvent is then stripped off and the remaining residue is heated for 1 hour at 50 ° on a rotary evaporator under a high vacuum. It resulted \ advantage a yellowish plastic material. Yield: 46 g = 89.2 # d. Th., Η = 10. Analysis: CHNM calc. 51.9 9.43 1.38 # 2036 found. 52.5 9.4 1.2 % 2300 "

Example 13

Analogously to Example 8, 29.5 g (0.25 mol) of α-methylstyrene and 4 * 1 g (0.025 mol) of ÄIBN are reacted in 125 ml of benzene. An oligomeric mixture with an N content of 7.1 $> » M _n = 440 is obtained
η = 2 - 3

Example 14

34.5 g (0.25 mol) of 4-chlorostyrene and 4.1 g (0.025 mol) of AIBN are reacted in 125 ml of benzene as in Example 8. A glassy, brittle product with an N content of 1.8% is obtained. 'η = 9-10
= 1320

10-9862 / 1972

Example 15

A mixture of 86.1 g (1 mol) of vinyl acetate, 16.4 g (0.1 mol) of AIBN and 500 ml of benzene is heated very quickly to the boil and then refluxed for 6 hours. The reaction mixture obtained is concentrated on a rotary evaporator. 90.8 g of a viscous residue with an N content of 3.03 # are obtained. M _n 920; η = 10.

Oligomers are obtained through lower concentrations of initiator with a correspondingly higher degree of polymerization, ζ. B. η = at 0.02 mol.

Example 16

Analogously to Example 5, 50 g of vinyl acetate, 200 ml of methanol and 16.4 g (0.1 mol) of AIBN are placed in an autoclave. Ethylene Ma is pressed atm to a pressure of 60 and the mixture is polymerized at 8O ⁰ O. This gives 121 g of reaction product having a melting range 32-39 ⁰ C. N-content 2.25% \ \ = 1250; η = 13 '

Vinyl propionate is being used in place of vinyl acetate with equal success and / or vinyl butyrate are used. Here too, when using the same molar amounts, olfeomers are also obtained an average degree of polymerization £ = 13 Example 17

A solution of 10 g of methyl methacrylate (0.1 mol) and 3.28 g AIBN (0.02 mol) in 90 ml of toluene are added over the course of 4 hours added dropwise to 400 ml of toluene heated to 100 °. After 1 hour Reaction time, the solvent is distilled off and "is obtained 11 g of an oligomeric mixture. The mean degree of polymerization is n = 5.5

109852/197 2

It can be seen from the gel chromatogram that a strictly poly-mer homologous series has been formed and that the reaction product contains far less than 3 % of compounds with a molecular weight of more than 2500. ..

Example 18 ',.

One mole of styrene and 0.1 mole of AIBN are dissolved in 150 ml of toluene and in the course of 4 hours in 200 ml of boiling toluene dripped. The reaction mixture is refluxed for 1 hour, then the solvent is stripped off under reduced pressure and the residue is ge for one hour at 40 ° in a high vacuum

keep. You get 96 G g = 81.5 <P d. Th. of oligomers • η = 9 89 N M. Analysis: 90 H , 65 1072 calculated! , 7 .7.93 2 , 8 1060 found: ₉ 0 8.1 2

Example 19

Analogously to Example 18, 0.9 mol of styrene and 0.1 mol of AIBN are dissolved in 350 ml of toluene and added to 200 ml of boiling toluene. 84.8 g of oligomers are obtained. "■ Analysis: -CH IM calculated? 89.7. 7.93- 2 ₉ 65 1072.

found; 88.6 8.21 2.8 '. 1030

Example 20

Analogously to Example 18, -0-, 7 mol of styrene and O ₉ I mol of AIBI are dissolved in 420 ml of toluene and "200 ml" of boiling toluene are added dropwise »69 g of oligomer are obtained £ = 7» "-"

Analysis 1 G 'H ■ I. . I.

calculated: 88.9. '7 ₉ θ7' 3.24 864 found! 873 QA 3A-- ■ '_ 790- -

1098S2 / I97

Example 21

Analogously to Example 18, 0.5 mol of styrene and 0.1 mol of AIBU in 400 ml of toluene dissolved and added dropwise to 200 ml of boiling toluene. After working up, 60 g of oligomers, η = 5

Analysis: calculated: C. 9 H H 26th M. found: 87 3 7 <93 4, 65 656 87 8.3 4, 700

Example 22

104 g (1 mol) of styrene and 41 g (0.25 mol) of AIBIT are in 900 ml Dissolved toluene and boiling in 400 ml over the course of 4 hours Toluene dripped. Then let simmer for another hour and then pulls off the toluene. The residue is treated in a high vacuum at 40 ° for 1 hour. 103 g = 77.3% of theory are obtained. .Th. of a viscous oil, 5 = 4

Analysis ι calculated: σ 3 7th H found: 86 3 7th , 98 85 , 9 •

M. 5.1 % 550 5.1 # 580

Example 23

39.3 g (0.25 mol) of 2-dimethylaminoethyl methacrylate and 4.1 g (0.025 mol) of AIBF are dissolved in 70 ml of toluene and im Added dropwise to 50 ml of boiling toluene over the course of 4 hours. It is then refluxed for a further hour, whereupon the solvent is withdrawn. After 1 hour of treatment in the

O ' m

High vacuum at 40 gives a yield of 41 g of a "

viscous oil with an average degree of polymerization of η = 10. Analysis: CH IT M

calculated: 61.8 9.45 9.85 1706

found: 61.4 9.4 9.3 1830

The 2-ethoxyethyl methacrylate reacts in the same way to an oligomeric product with η = 10.

109852/1972

Example 24.

46.1 g of 2-ethylhexyl acrylate (0.25 mol) and 8.2 g (0.05 mol) of AIBN are dissolved in 200 ml of toluene and added dropwise to 75 ml of boiling toluene in the course of 4 hours. The further reaction and work-up are carried out in the same way as in Example 22. Yield 48 g = 89% d. Th., Η = 5 '
Analysis: CHNH

calculated: 71.6 10.6 '2.65 1056 found: 70.5 9.8 2.7 1020

In the same way, the acrylic acid cyclohexyl ester gives a oligomeric product with η = 5

Example 25

Analogously to Example 24, 63.6 g (0.25 mol) of lauryl methacrylate and 4.1 g (0.025 mol) of AIBN, dissolved in 120 ml of toluene, are added dropwise to 20 ml of boiling toluene. After working up, a viscous oil is obtained, η = 10 »
Yield 60g = 89.5 %
Analysis: G

calculated: 75.3 found: 76.2

A likewise oily oligomer with η = 10 is obtained in an analogous manner Way from the methacrylic acid cresyl ester.

Example 26

27.8 grams (0.25 moles) of N-vinyl pyrrolidone and 8.2 grams (0.05 moles) of AIBN are dissolved in 100 ml of toluene, added dropwise in the course of 2 hours to 50 ml of boiling toluene. Analogously after work-up Example 22 gives 34 g of a highly viscous oil, 5 = 5. Analysis: C .H N 0 M

calculated: 66.2 8.25 14.2 11.6 691 found: 66.4 8.4 14.1 ■ 11.2 710

H 1 .05 $> M. 11 , 7 1 1 iL
, ι ι ° 2676 11 , 9 2430

109852/1972

By reducing the proportion of initiator up to 0.005 mol ⁶ Jt , oligomers with a corresponding degree of polymerization of up to η = 50 are obtained. ''

According to the rule given above, one also obtains from N-vinylimidazole, N-vinylphthalimide, vinylpyridine, vinylquinoline and vinylthiophene oligomers with η = 5.

Example 27

13.25 g (θ, 25 mol) of acrylonitrile and 12.9 g (θ, 05 mol) of 2.2 ^t -Azo-bis-isobutyric acid ethyl ester are dissolved in 50 ml of toluene and this solution is added dropwise to 50 ml in the course of 3 hours boiling toluene. The reaction mixture is allowed to react under gentle reflux for a further 12 hours while passing nitrogen. Subsequently, the solvent is stripped off and the residue holds about 1 hour at about 80 ⁰ C under high vacuum (l Torr) to all of the volatile impurity © »to remove. 19 g of a clear, brown, viscous residue remain. ,
Yield: 19 g; -. »74.8 % of theory, η = 5

N 0 U _n saponification number

14.1 12.9 495 230 13.5 13.0 495 203

In the same way, methacrylonitrile is converted to oligomers with η = 5 «

Example 28

104 g of styrene (1 mol) and 51.6 g of 2,2 »-azo-bis-isobutyric acid diethyl ester (0.2 mol) are dissolved in 150 ml of toluene and the solution is added dropwise to 50 ml of boiling toluene over the course of 4 hours. The mixture is then allowed to react for a further hour at the boiling point, the solvent is then stripped off and the residue is treated on a rotary evaporator for 1 hour in a high vacuum (1 Torr) at ⁰

109852/1972

Analysis: C. 5 7th calculated; 65, 1 7th found: 66 H , 48 , 9

g = 89.5? 26- -
IS »" 5. O VJl 2030589 Yield: 136 C. i d. Th., 5 = ,1 Analysis: 83, H 8th M _n calculated: 82, 8.3 8th 750 found: 8.5 825 ,1 , 9

An analogous product is obtained in approximately the same yield if instead of the azo compound mentioned, 0.2 mol of 2,2'-azo-bis-2-methyl-butyric acid diethyl ester used. The two end groups of this oligomer with η = 5 have the formula

2 ^H 5

Example 29

A solution of 56.1. g acrolein (1 mol) and 32.8 g AIBN (0.2 mol) 900 ml of toluene are added dropwise to 50 ml of boiling toluene in the course of 4 hours. Then leave the reaction. 1 hour at Continue to boiling temperature, then cools the solution and removes it on a rotary evaporator in vacuo at 40 ° and then the solvent in a high vacuum. The result is a light brown, highly viscous mass, η a 4 - 5

Analysis: CH NO M

η = 4 66.6 7.8 7.8 17.7 360 * calculated: _{5 = 5 66> 3 7>? 6>? 5 19> 2 416}

found: 66.2 8.4 7, "1 17.7 400 Example 30

Analogously to Example 29, 70.1 g of methyl vinyl ketone (1 mol) are used with 32.8 g of AIBN (0.2 mol) µm. 77 g (79.1% of theory) are obtained of a tough brown oil, - S = 5

Analysis: C H "N OM calculated: 69.1 8.64 5.98 16.54 486, found: 69.1 8.8 6.0 15.6 423

1098 52/1972

Example 31

100.2 g vinyl isobutyl ether (1 mol), and 32.8 g AIBN (0.2 mol) it is dissolved in 500 ml of toluene and this solution is added dropwise to 50 ml of boiling toluene in the course of 4 hours. Afterward it is allowed to reflux for a further 60 minutes and then the solvent is removed at 70 ° in vacuo on a rotary evaporator.A light brown, viscous oil is obtained. η = 1 - 2

Analysis: 'C HN OU

calculated: η = 1 71.2 10.2 11.8 6.8 236 n ~ 2 71.4 10.7 8.3 9.5 336

found: 70.1 10.2 11.2 8.6 298

Example 32

96.9 grams (1 mole) of vinylidene chloride and 32.8 grams (0.2 moles) of AIBN will be used dissolved in 200 ml of benzene. This solution is dripped in the course of .4 hours in 50 ml of boiling benzene. In the course of the reaction, the telechelic oligomer partially precipitates out as a white-yellow precipitate. The solution is left after the dropping has ended react under reflux for another hour. The solvent is then drawn off under reduced pressure and the residue is kept another 4 hours at 40 ° on a rotary evaporator in a high vacuum. A product of η = 5 is obtained.

Example 33

In the manner indicated in Example 34, 85.1 g (l mol) of methacrylic acid amide are reacted with 32.8 g (0.2 mol) of ιAIBN. You get after working up 44 g of a white mass η = 7

Analysis: 59 C. H N 0 calculated: 59 , 2 8.4 17.2 15.3 found: A. 8.7 16.9 15.0

109862/1972

- 38.-

Example 34

85.1 g (1 mol) methacrylic acid amide and 82.1 g (0.5 mol) AIBN
are dissolved in 750 ml of dioxane and added dropwise to 100 ml of boiling dioxane in the course of 2 hours. After the end of the dropwise addition, which is accompanied by increasing turbidity of the reaction solution, the mixture is refluxed for a further 1.5 hours. After cooling, the precipitated white product (23.5 g of polymethacrylamide) is filtered off, the mother liquor is concentrated under reduced pressure and the residue is treated on a rotary evaporator
at 70 ° for 4 hours in a high vacuum · A white, waxy mass is obtained.
Yield 114 g = 74.4 # of theory η «3« 4

Analysis: η = 3 61 C. E. [' 17th N 12th 0 M. calculated: η β 4th 60 , 5 8th, 45 17th , 92 13th , 3 391 61 , 5 8th, 42 17th , 69 12th , 5 476 found: ,1 8th, 7th 'Λ ,8th 399

Example 35

A mixture of 130.1 g (1 mol) of itaconic acid, 32.8 g (0.2 mol) of AIBN and 750 ml of dioxane is added dropwise to 50 ml of boiling toluene over the course of 4 hours
146 g are obtained under reflux and working up as in Example 34
a yellow-white, waxy mass. K = 5.

109852/1972

Claims (22)

Claims " (i./Process for the production of telechelic oligomers with two identical end groups, characterized in that one radi— Italic polymerizable © monovinyl compounds, except Olefins with more than 2 carbon atoms, with a symmetrical,. radical donating azo compound converts, with the concentration the initiator fragments is adjusted so that when the desired degree of polymerization is reached between 1 and 200 a complete chain termination takes place exclusively through initiator fragments. 2. The method according to claim 1, characterized in that 0.5 to 50 mol ^c / o of the initiator are used, based on the monovinyl compounds used. 3. Process according to claims i and 2, characterized in that the initiator fragments are formed thermally. 4. The method according to claims 1 - 3, characterized in that that the corresponding to the desired degree of polymerization Amount of the azo compound is heated together with the monomers at least to a temperature at which the half-life the initiator disintegration is about 4 hours. 5. The method according to claims i - 4, characterized! that the reaction is carried out in an inert organic solvent. 6. The method according to claim 5, characterized in that the solvent is benzene and / or toluene and / or tert-butanol and / or dioxane is used. 109852/1972 Zl 7. The method according to claims 1-6, characterized in that that the implementation is carried out in thin heated tubes will. 8. The method according to .Ansprüche 1-7, characterized in that that azo-bis-isobutyronitrile is used as the azo compound will. 9. Process according to claims 1-9 »characterized in that the azo compound is 2,2'-azo-bis-2-methylbutyronitrile, 2,2'-azo-bis-isobutyric acid alkali salts, the associated amide or the ester, in particular the corresponding methyl and ethyl esters, 2,2'-azo-bis-2-methylbutyric acid alkali salts, the associated amide or the esters, in particular the corresponding methyl and ethyl esters, or 4} 4 ^l -azo-bis-4-cyanopentanoic acid whose di-Na salt or their alkyl ester is used. 10. The method according to claims 1 - "9 ·, characterized in that the monovinyl compounds are ethylene, styrene and / or (Meth) acrylic derivatives can be used. 11. The method according to claims 1 - 1O _$ characterized in that a mixture of ethylene and vinyl acetate is used as monovinyl compounds. - 109852/1972 12. Tele-helical oligomers with narrow molecular weight ratios - division and. with an average degree of polymerization of - 200, the chains of which are monovinyl compounds excluded Olefins with more than 2 carbon atoms are the basis and both chain ends are characterized by identical radical fragments symmetrical azo compounds are substituted. 13. Telechelic oligomers of the formula I. ι ¹ R- (CIi ₂ - C -.) _Ä -R where * R is the radical fragment of a symmetrical azo link
R. Hydrogen or lower alkyl, in particular methyl
R _{2 is} hydrogen, phenyl or substituted phenyl, -COOR ₃₁ -COR ₄ , -CHO, -CN, or -OR ₅ Rg hydrogen; Alkyl with up to 18 carbon atoms, which can also be interrupted by heteroatoms (θ, N, S); Cycloalkyl with 3-7 carbon atoms; Phenyl or substituted phenyl;
R. NIL · and the associated mono- and dialkyl derivatives (Alkyl groups with up to 18 carbon atoms); CO-alkyl (Alkyl groups with up to 18 carbon atoms) and CO-phenyl, the phenyl groups also being substituted can;
Rg alkyl or aliphatic acyl, each with up to 18 carbon atoms;
η is a number between 1 and 200, with the proviso that R _{1 is not methyl when R 2 is} hydrogen. 109852/1972 14. Telechelic oligomers of the formula II R - (CH ₂ - CH) _n - R R ₉ II wherein R * is the radical fraction of a symmetrical azo link R "hydrogen or phenyl" η 1 - 200 means.
15. Telechelic oligomers of the formula III - C) _n - R R _fi ⁶ III wherein R the radical fragment of a symmetrical azo « link R. Hydrogen or methyl R ₆ COO-alkyl with up to 18 carbon atoms; CONH ₂ ; CN; CHO, η 1-200 means.
16. Telechelic oligomers of the formula IV R - (CH ₂ - CH) _n ™ R wherein R and η have the meaning given in claim 14 « 109852/1972 17. Telechelic oligomers according to claims 13 to 16, dadruch characterized in that R is one of the following radicals a - c: C - CN CH ₃ R ₇ C - COOR _D I. - C - CH ₂ - CH ₂ - COOR ₉ CN wherein R- methyl or ethyl, Rg is an alkyl radical with up to 6 carbon atoms and R _{9 is} hydrogen, alkali metal (Na, κ) or alkyl with up to 6 carbon atoms means. 18. Telechelic oligomers according to claims 13-17, characterized in that. R denotes the radical -c (CH ₃ ) ₂ CN. 19. Telechelic oligomers of Formula V CH ₃ NC-C- (CH ₂ - CH ₂ ) _n - C - CN CH ₃ CH ₃ . wherein η is a number between 5 and means. 109852/1972 20. Telechelic _t 01igomere of formula VI OH-CH,. I 5 j 3 NO -C - (CH ₂ - CH) _n - C - CK \ gh, 'Ai i: 3 gj - ^Η 3. , wherein η means a number between 1 and $ 0 . 21. Telechelic O-ligomers of the formula VII CH, CH ₅ NC -9 - (CH ₂ - C -) _n - C - CN COOCH ₅ C wherein η is a number between 1 and 50. 22. Telechelic oligomers of the formula VIII H- CH ⁵ I. NC -C - (CH ₉ - CH L - C - CN I II " ^{¥ I3CI} CH ₅ COOCH ₅ GH ₅ wherein η is a number between 1 and 50. 109852/1972